A novel pentadecatungstate, [H 6Ce 2(H 2O)Cl(W 5O 18) 3] (7-) ( 1), constructed by a dinuclear cerium unit and 15-member ring WO 6 units was prepared and characterized by single-crystal X-ray diffraction. Polyanion 1 exhibits blue photoluminescence with an emission maximum at 488 nm, which is characteristic of cerium(III) transitions from 5d to (2)F 5/2 states. Furthermore, the study of the electrochemical property investigation of 1 shows two reversible redox peaks ascribing to two-electron processes.